Subtitling of processed photographic materials

ABSTRACT

Graphic information, such as a subtitle, is recorded on a recording material, such as a motion picture film, by means of an externally applied surface layer of an organic film-forming polymer adapted to undergo a differential increase in solubility in an appropriate solvent as a result of imagewise heating so that, by contacting the differentially heated and thereby solubilized surface layer with the appropriate solvent, the relatively more soluble areas can be selectively removed, leaving the underlying areas of the recording material exposed. Heating can be effected directly within the surface layer by uniformly distributing throughout the polymer forming the same finely divided pigment or dye which, when exposed to a radiation image such as from a copying light, preferably a flashlight, absorbs such radiation and converts the same directly into heat. Where sufficient pigment or dye is present as to impart opacity to the surface layer, preferably an optical density of at least one, the graphic information can be formed by selective removal of the nonimage areas of the surface layer leaving an opaque relief image thereof to constitute the graphic information. Alternatively, the recording material with the partially removed surface layer thereon can be contacted with a liquid effectively bleaching the colorant material, i.e., the metallic silver or dye image, therein or, in the case of motion picture film, carrying a developed silver halide emulsion layer disintegrating the binder of that layer, or contains a dye which penetrates the exposed regions of the recording material.

Attorney-William J. Daniel United States Patent Brinckman et al.

[ Feb. 29, 1972 [54] SUBTITLING OF PROCESSED PHOTOGRAPHIC MATERIALS [72]Inventors: Eric Maria Brinckman; Louis Achilles Meeussen, both ofMortsel, Belgium [73] Assignee: Gevaert-Agfa N.V., Mortsel, Belgium [22]Filed: Mar, 27, 1969 211 App]. No.: 810,959

[30] Foreign Application Priority Data Mar. 27, 1968 Great Britain..l4,779/68 [52] US. Cl ..96/36, 96/43, 250/65.1, 96/1 15 R [51] lint.Cl. ..G03e 5/00, G030 5/04 [58] Field of Search ..96/36, 43, 44, 115,27; 250/65.l

[56] References Cited UNITED STATES PATENTS 1,769,599 7/1930 Neidich..96/36 2,051,603 8/1936 l-Iruska ...96/43 2,915,581 12/1959 Pajes..96/43 FOREIGN PATENTS OR APPLICATIONS 754,990 8/ 1956 Great Britain..96/ 36 Primary ExaminerNorman G. Torchin Assistant Examiner-JohnWinkelman [5 7] ABSTRACT Graphic information, such as a subtitle, isrecorded on a recording material, such as a motion picture film, bymeans of an externally applied surface layer of an organic film-formingpolymer adapted to undergo a differential increase in solubility in anappropriate solvent as a result of imagewise heating so that, bycontacting the differentially heated and thereby solubilized surfacelayer with the appropriate solvent, the relatively more soluble areascan be selectively removed, leaving the underlying areas of therecording material exposed. Heating can be effected directly within thesurface layer by uniformly distributing throughout the polymer formingthe same finely divided pigment or dye which, when exposed to aradiation image such as from a copying light, preferably a flashlight,absorbs such radiation and converts the same directly into heat.Where'sufficient pigment or dye is present as to impart opacity to thesurface layer, preferably an optical density of at least one, thegraphic information can be formed by selective removal of the nonimageareas of the surface layer leaving an opaque relief image thereof toconstitute the graphic information. Alternatively, the recordingmaterial with the partially removed surface layer thereon can becontacted with a liquid effectively bleaching the colorant material,i.e., the metallic silver or dye image, therein or, in the case ofmotion picture film, carrying a developed silver halide emulsion layerdisintegrating the binder of that layer, or contains a dye whichpenetrates the exposed regions of the recording material.

19 Claims, 1 Drawing Figure SUBTITLING OF PROCESSED PHOTOGRAPHICMATERIALS I The present invention relates to a method for recording andreproducing graphic information on processed photographic material, moreparticularly to subtitling of motion pictures.

Various methods for subtitling processed silver halide black-and-whiteor color movies are known.

According to such known techniques a side part or the bottom part ofphotographic images producedby silver halide black-and-white or colorphotography is provided with text.

According to one technique of subtitling the emulsion layer is removedat the areas corresponding with the text characters, e.g., by tearingout. For this purpose printing blocks carrying the text in relief arepressed against the previously wetted emulsion layer and then separatedtherefrom, thus tearing out the emulsion down to the support incorrespondence with the relief. However, such procedure is rathercumbersome and incurs the risk of bad reproduceability and damage to thefilm. Too strongly hardened an emulsion cannot be torn out as deeply asthe support, so that the text is not reproduced in a sufficiently whitetone.

According to another technique, the emulsion side of a processed film iscovered with a wax layer, which in accordance with the text markings, ispressed back by means of metal letterpress dies to allow the binder ofthe emulsion, image silver or image dye(s) to be attacked locally.Subsequently the remaining parts of the wax layer are dissolved away.The manufacture of metal letterpress dies with minute characters needsgreat care, and the successive pressing steps wherein the emulsion layeris made free for local attack cannot be carried out at a high rate andwithout loss of sharpness of the characters. Moreover, the need toremove the remaining parts of the wax layer with an organic solvent,e.g., naphtha, makes that technique less attractive.

According to another technique, described in the U.K. Pat. No. 754,990,a varnish layer, which is resistant to an etching liquid containing analkali metal of alkaline-earth metal hypochlorite, is applied to theimage-containing emulsion and is then covered itself by alight-sensitive emulsion layer. The light-sensitive top layer is firstexposed by light transmitted through a support bearing transparentcharacters of the subtitles, and then developed. Subsequently, thegelatin of the emulsion layer is degraded at the image areas containingsilver, e.g., by means of a commonly used oxidizing solution containingdichromate. The varnish layer is then dissolved away at the areas, wherethe gelatin-containing top emulsion layer was removed. Subsequently theimage silver or image dye in the subjacent emulsion layer(s) is etchedor bleached away by means of an aqueous hypochlorite solution.

' Alternatively, the top emulsion layer can be exposed to lighttransmitted through a support bearing the subtitles as an opaque text,then be treated in a tanning-developing bath and washed away at theunhardened areas, whereupon the above procedure of imagewise removingthe varnish and etching the emulsion layer is applied.

Obviously, the application of a varnish layer and a light-sensitiveemulsion layer to a processed silver halide material is extremely timeconsuming. The coating of a light-sensitive silver halide emulsion canonly be effected in the dark and the emulsion requires special care inits preparation. Furthermore, the cumbrous processing impedes thepractical realization of this technique.

It has been found now that graphic information can be recorded simplyand adequately on photographic materials containing black-and-white orcolor images, e.g., motion pictures, by the steps of:

l. applying to the image side of a processed photographicblack-and-white or color material an overlayer, which by the action ofheat becomes more permeable for and/or removable by an appropriatetreating liquid,

2. and inforrnationwise heating said overlayer so that the informationis recorded in terms of a difference in permeability for and/orremovability by an appropriate treating liquid of different portions ofsaid overlayer.

By the term appropriate treating liquid" is meant a liquid, whichselectively permeates, degrades or dissolves the heated portions of saidoverlayer. The selective removal may be helped by a soft rubbing of theoverlayer while wetting it with the treating liquid.

The selection of an appropriate treating liquid can be carried out bytests in which heated and nonheated portions of an overlayer of thecomposition in view are contacted by a liquid to be tested and in which,after a few minutes, the amount of the composition dissolved and/orsoftened or of the liquid penetrated into (penetration depth) each ofthe portions, is determined. 1

The inforrnationwise change in the overlayer effected by theinforrnationwise heating enables a developed record of the informationto be formed by treating the photographic material nondifferentiallywith a treating liquid which penetrates or removes portions of theoverlayer which have been rendered permeable or soluble, or which havebeen rendered more penneable or more soluble, by the treating liquid.Depending on the composition of the photographic material and/or theoverlayer, and of the treating liquid, the visible record may be formedby parts of the overlayer itself, or such record may be formed by virtueof a physical and/or chemical change effected in an underlying layer,e.g., a silver halide layer, by the treating liquid. The image areasforming the developed record may be of higher or lower optical densitythan the surrounding areas.

A development involving physical and/or chemical attack of portions ofthe photographic material, e.g., portions of a developed silver halideemulsion layer, may be achieved by using as treating liquid, a liquidwhich has the property of etching, degrading, dissolving, bleaching,discoloring or coloring some or all of the ingredients of thephotographic material, e.g., so that in the areas where such liquidpenetrates to the photographic material, the optical density of animagewise exposed and developed silver halide emulsion layer isincreased or decreased. The liquid will only exert its influence onthose portions of the photographic material which are not shielded bythe portions of the overlayer which are still impermeable or onlyslightly permeable by the treating liquid. After the desired action bythe treating liquid has taken place, the overlayer, or if portions ofthe overlayer have already been removed by the treating liquid, then thestill remaining portions of the overlayer, can be removed from thephotographic material.

In general, positive motion pictures are subtitled by reducing theoptical density of the photographic material in correspondence with thegraphic information to be reproduced. This can be achieved by using atreating liquid by which the silver metal particles constituting thesilver image of a developed silver halide layer are bleached or etchedaway. Alternatively, the dyes of a positive color print obtained indeveloped silver halide color material can be bleached, degraded, andwashed away in accordance with the subtitle to be produced. The binderof the recording layer, e.g., a proteinaceous binding agent, such asgelatin contained in common silver halide recording materials, can bedegraded with liquids comprising hydrogen peroxide or alkali metalhypochlorites (ref. P. GlatkidesPhotographic Chemistry Vol. lI-FountainPress London, pp. 668-669).

Subtitle indicia of higher optical density than the surrounding areascan of course also be produced by the action of a treating liquid whichaffects the portions of the photographic material from which thecovering portions of the overlayer have been removed or which arecovered by portions of such overlayer which have been rendered permeableor more permeable to the treating liquid by the inforrnationwise heatingstep. Thus, a treating liquid can be used which is a dye solution.According to another technique, subtitle indicia of higher opticaldensity than the surrounding areas can be formed by portions of theoverlayer itself. Thus, the composition of the overlayer may be suchthat this layer is an opaque colored or black layer and the latentrecord of the heat pattern can be developed just by using a treatingliquid which washes away the portions of the overlayer which aresufficiently soluble in or permeably by the treating liquid, i.e., theportions of such overlayer which have been heated.

The formation of a subtitle in the form of dark or opaque markings is ofspecial interest in the subtitling of negative or duplicating negativemotion pictures, which are used to print release prints.

Opaque graphic markings can be formed by introducing a silver salt orsilver salt complex into the photographic material in areas where theoverlayer has'been removed or rendered permeable or more permeable andby reducing the said salt or complex to silver metal or by introducingcolorless color couplers, which react with ingredients absorbed in oneor more layers of the material. A color reaction can be catalyzed by acatalyst either present in said layer(s) or in an aqueous treatingliquid. It is equally possible to produce colored or opaque imagemarkings by introducing through the openings or permeabilized portionsof the overlayer a dye solution containing a dye or a mixture of dyesabsorbing light of a part or the whole visible spectrum. In order toprevent lateral diffusion, said dye(s) are preferably used incombination with mordanting agents, e.g., those known from theimbibition printing process, wherein acid dyes are applied. Suitabledyes and mordanting agents are described, e.g., in the UK. Pat. No.830,189, and the U.S. Pat. No. 3,234,025.

Suitable compositions for preparing a heat-sensitive overlayer orsurface layer of use according to the present invention are described inthe U.S. Pat. Ser. No. 763,354, filed Sept. 27, 1968 the content ofwhich should be read in conjunction herewith, and is deemed to form partof the present disclosure.

Compositions and compounds which are suited for producing an overlayerof use according to the present invention are described hereinafter inTable l TABLE 1 1. galactomannan, which is a glucoside having thefollowing structural units:

CHaOH H l*" O :1.

CHgOH .L

2. cationic hydroxypropyl starch (the viscosity of a 5 percent solutionin water at 25 C. is preferably 5 P);

3. hydroxypropylmethylcellulose preferably having a DS methoxyl 1.7-1.8;DS hydroxypropoxyl 0.1-0.2; the viscosi ty of a 2 percent solution inwater at 20 C. is preferably 45 P. DS Degree of Substitution);

4. cellulose acetate butyrate preferably having a DS acetate 0.4-0.5; DSbutyrate 2.4; the viscosity of a 20 percent solution in acetone at 20 C.is preferably 17 P;

5. melamine-formaldehyde resins, methylol-melamine resins,

gallic acid, barbituric acid, 2,4-dihydroxybenzoic acid,pamino-salicylic acid, stearic acid, itaconic acid, mandelic acid,succinic acid, methacrylic acid and polyacrylic acid;

6. anionic water-soluble urea-formaldehyde resins, which after coatingare hardened (preferably weakly) by a moderate nondifferentialheat-treatment or simply by keeping the coated recording layer for someweeks at room temperature prior to recording;

7. a resorcinol-formaldehyde resin soluble in ethanol or in a mixture ofethanol and water, and which becomes soluble in pure water by heating;

8. a composition containing a water-soluble polyvinyl alcohol mixed witha hardening agent containing (a) reactive carbonyl group(s), e.g.,formaldehyde or l,4-dichloro-2,3-butanedione; 9. a compositioncontaining a water-insoluble polymer comprising a basicnitrogen-containing heterocyclic nucleus, e.g., a poly( 1,2-dihydro-2,2,4trimethylquinoline) (see for such type of polymer theU.S. Pat. No. 2,718,517 and also our UK. Pat. application No. 4276/68)and an organic or inorganic compound with acidic character, e.g.,hydrogen chloride, acetic acid or a polymer or copolymer of anafiethylenically unsaturated compound containing a carboxylic orsulphonic acid group, e.g., polyacrylic acid, polystyrene sulphonicacid, copoly(methacrylic acid/styrene), copoly(acrylic acid/N-vinylpyrrolidone), copoly(acrylic acid/acrylamide), copoly(methacrylicacid/methyl methacrylate), or methacrylic acid, the compound having anacidic character being preferably used in a weight ratio of 20-500percent in respect of the poly( l,2-dihydro-2,2,4-trimethyl-quinoline),more preferably in a weight ratio of 50-300 percent;

10. a water-soluble polymer or copolymer of an a, fi-ethylenicallyunsaturated compound containing one or more carboxylic acid groups,e.g., polyacrylic acid, in admixture with a reactive compound forming aproduct with said polymeric compound, which product is less soluble inwater than said polymeric compound and that on heating is dissociatedagain resulting in an increase of the solubility in water of thecomposition. Suitable reactive compounds for that purpose are cobaltnaphthenate and 2,4-dihydroxy benaophenone;

l 1. alginic acid ester, e.g., 2-hydroxypropyl alginate;

12. novolak type resins e.g., a monohydroxybenzene-fonnaldehyde novolaksuch as phenol-formaldehyde, cresol-formaldehyde,p-tert.butylphenol-formaldehyde or mixed monohydroxybenzenehomologue-formaldehyde novolak resins;

l3. polymers including copolymers containing azo groups linked through acarbon atom to a nitrile group, preferably polymers comprising groups ofthe following structure:

The preparation of polymers containing such groups is described inMakromol. Chem. 103 (I967) p. 301-303. Typical representatives arepolyesters and polyarnides containing the following structural group intheir recurring units:

wherein:

R represents a lower alkyl group, and

Y a bivalent hydrocarbon radical preferably an alkylene radical of lessthan four carbon atoms.

Useful good results are obtained with a polyester or a polyamide havingthe following recurring units respectively:

L Ha H3 14. poly(N-vinylpyrrolidone);

l5. crude and/or bleached shellac optionally in admixture with aperoxide compound, e.g., cumene hydroperoxide;

16. poly-l ,2-dihydro-2,2,4-trimethyl-quinoline;

17. poly(N-vinylpyrrolidone) in admixture with a melamineformaldehyderesin containing methylol groups;

18. a composition containing polyvinyl alcohol or a partially hydrolyzedpolyvinyl acetate mainly containing vinyl alcohol latex undergoes anincrease in solubility in a C C alkanol byheating;

21. a copoly(styrene/acrylate ester) applied from alatex, preferably acopoly(styrene/ethyl acrylate) (20/80);

22. a composition containing a copoly(butadiene/styrene) and anortho-quinone-diazide compound, e.g., as described in the U.K. Pat. No.1,116,737, e.g., 2,2-bis(2-bromo-6-diazo-2,4-cyclohexadiene-4-yl-l-one)-propane and the ortho-quinonediazidecompounds splitting off an acid on heating as described in the BelgianPat. No. 674,218; 23. a composition containing a phenol-formaldehyderesin and a peroxide compound, e.g., cumene hydroperoxide.

By the term Novolak" according to British Standard 1755-1951 has to beunderstood soluble, fusible, synthetic resins produced from a phenol andan aldehyde, having no methylol groups in the molecule and thereforeincapable of condensing with other novolak molecules on heating withoutthe addition of hardening agents."

Information about the preparation and structure of novolaks can be foundin C. Ellis, The Chemistry of Synthetic Resins, Vol; 1 (1935) Reinholdpublishing Corporation, New York, pp. 303309 and in Houben-Weyl,Methoden der organischen Chemie, 4. Auflage, Band XlV/2 MakromolekulareStoffe, Teil' 2, p. 201 seq.

Overlayers containing the compounds or compositions listed in the aboveTable l undergo an increase in solubility in an appropriate solvent upona proper intensive heating. Thus the compound or compositions 1 to 11show an increase in solubility in water; the compounds 12 to 15 anincrease in solubility in an alkaline aqueous medium, e.g., an aqueoussolution having a pH 12, and in the case of the compound 13 also arisein solubility in an ether-type solvent, e.g., ethylene glycol or themonomethyl ether of diethylene glycol and in the case of the compound 15also a rise in solubility in a C -C alkanol; the compounds 16 to 20 arise in solubility in a C -C alkanol, e.g., ethanol and the compound 20also a rise in solubility in a lower ketone containing C,C carbon chainslinked to the carbonyl group, e.g., acetone, as does compound 21', thecompositions 22 and 23 an increase in solubility in chlorinatedaliphatic hydrocarbons, e.g., methylene chloride and carbontetrachloride.

In order to make the overlayer sufficiently insoluble in the processingliquid, e.g., an aqueous etching liquid for silver metal, it isnecessary in particular cases, i.e., in the case of the above-mentionedmelamine resins, to dry the applied layer nondifferentially for acertain time at a temperature between 50 and 130 C., e.g., for 5 hoursat C.'or for 5 minutes at C. The optimal processing time and temperatureshould be detennined experimentally, since too strong and too lengthy aheating causes an irreversible insolubility in water,

which by a rather short high-intensive heating cannot be an nulledanymore.

The overlayer may comprise suitable ingredients such as pigments, e.g.,carbon particles or metal particles, reinforcing or filling agents, andunreactive inorganic solids of small size including glass, mica'Qsilica,bentonite, etc. Preferably, these ingredients are used in a weight ratioin respect of the above selected polymers not surpassing 20 percent.

The heated portions'of the recording layer containing the compounds orcompositions l to 11 described above in Table 1 can be removed moreadequately when containing a certain amount of water-soluble compounds,with the proviso, however, that the selectively of the washing away isnot substantially disturbed. Such compounds are, e.g., polyacrylic acid,polyacrylamide, poly(N-vinylpyrrolidone) and polyoxyethylene resins.

- The application of heat to the overlayer in correspondence with thegraphic information to be reproduced can be achieved in different ways.Thus, it is possible to heat the overlayer by bringing it in contactwith image markings of an original containing the graphic information tobe reproduced and simultaneously exposing said markings to infrared orhighintensity visible radiation, which is absorbed bysaid markings Whenusing metal letterpress dies, the heating may be can ried out by meansof a high frequency alternating current passing through the parts of theoverlayer brought into contact 'with the conductive relief parts of thedie. In this case the backing of the processed recording material standsin contact with an electrode and the overlayer contains a sufficientamount of high-frequency heatable material, e.g., iron particles.

Selective internal heating of the overlayer used according to thepresent invention is, however, preferably realized by exposing-anoverlayer, containing infrared and/or visible lightabsorbingsubstance(s) converting absorbed light into heat, to infrared radiationand/or visible light modulated a'ccording to the pattern to bereproduced.

Some specific examples of substances absorbing visible light andinfrared radiation and converting said light or radiation into heat are,i.e., finely divided carbon particles, e.g., carbon black and heavymetals in finely divided state, e.g., silver, bismuth, lead, iron,cobalt, and nickel, oxides and sulphides of these metals, e.g.,manganese dioxide, magnetic iron oxide (Fe O chromium (ll) oxide, cobaltsulphide, nickel sulphide, lead sulphide, and pigments and dyes such asPrussian blue (C.1. Pigment Blue 27), chlorinated copper phthalocyanine(CI. Pigment Green 7) or indigo (C.l. Vat Blue 1). The particle size ofthese substances preferably does not exceed 0.1 41..

Methods and apparatus by which the recording material can be exposed toan original when using the heat-generating property of said substancesare described in the published Dutch Pat. applications Nos. 6,606,719,6,414,226, 6,506,548, 6,607,637 and 6,608,504.

1f the overlayer contains substance(s), which abs0rb(s) copying light(infrared radiation and/or visible light) and convert(s) it into heat, acontact exposure of high intensity and short duration (preferably lessthan 10 sec.) is preferably applied. The original, is, e.g., a negativetransparency of the text 7 fuse into the surface layer, which isheated-only internally by the light absorbed in the light-absorbingsubstances contained therein. Preferably the concentration of saidlight-absorbing substances is such that at least 50 percent of the lightto which the overlayer is exposed is absorbed.

Suitable radiation sources producing copying light that can be convertedinto heat necessary for imagewise increasing the permeability, thesolubility and/or swellability of the surface layer containinglight-absorbing substances, which convert the copying light into heat,are so-called flash lamps. Good results are obtained with xenon gasdischarge lamps with an exposure time of 10 to seconds. Details on acopying device containing such a discharge lamp can be found in theBelgian Pat. No. 664,868. I

- If the emitted energy is focused onto a relatively small heatsensitivearea, e.g., having the size of an image (one picture) of a motionpicture film, a gas discharge lamp with a relatively low-energy outputcan be used. For instance, for copying a text on 18 mm. X 24 mm. motionpicture image a flash lamp with an energy output of 40 watt.sec. willsuffice. According to the type of thermopermeabilizable substanceheat-sensitive surface layers having an optical density of at least 1,resulting from the presence in the recording layer of light-absorbingsubstances converting absorbed light into heat, require a light energyof .at least 0.1 watt.sec/sq.cm. to realize a detectable imagedifferentiation. In most cases, an exposure of 0.5-1.0 watt. sec./sq.cm.yields satisfactory results.

The exposure may of course be carried out progressively orintermittently, e.g. with (a) flash lamp(s) yielding an overlappingintermittent exposure. Successive overlapping exposures are not harmfulsince no further change in the image differentiation is obtainedthereby. As an example of progressive exposure the transparent textoriginal can be scanned, e.g., with a high-intensity light beam, e.g., alaser beam, which rapidly linewise scans the original, or it can beexposed progressively through a slit, wherein, e.g., copying light isfocused from a tubelike radiation source.

Self-evidently, the heat-sensitive surface layer before or during theproduction of the imagewise heat differentiation can be subjected to anoverall heating to a certain temperature below the temperature at whicha substantial increase in permeability, solubility and/or swellabilityto a selected treating liquid takes place. In this way less imagewisesupplied heat energy is required to produce the desired increase inpermeability, solubility and/or swellability.

After production of the imagewise differentiation in permeability,solubility and/or swellability for an appropriate treatingliquid, thesurface layer is brought into contact with the selected liquid and,e.g., softly rubbed with a foamed rubber sponge, to remove selectivelythe heated portions. When a transparent subtitle has to be produced, thebinder of the emulsion layer, e.g., gelatin, can be disintegrated andthe image silver and/or the dyes present in the processed silver halideemulsion layer(s) can be removed, e.g., by means of an aqueous solutionof an hypochlorite of an alkali or alkaline earth metal.

Subtitling of a silver image picture can also proceed by bleaching thesilver without affecting the gelatin binder by using a conventionalbleaching bath and a subsequent'fixing bath, or by using a combinedbleaching-fixing solution.

In order to illustrate the subtitling process of a motion picture filmaccording to the invention, a diagrammatic section of a processing unitsuited for continuous subtitling is represented in the accompanyingdrawing. In said diagram the motion picture film l, e.g., a positiveblack-and-white or a color film, is unwound from a takoff roll 2 and bymeans of the 1 guiding rollers 3, 4 and 5 introduced into a coating tray6,

wherein the emulsion side of the film l is coated with a composition 7,which on drying in the ventilated drying channel'8 yields aheat-sensitive surface coating of the type described hereinbefore.

The motion picture film coated with its heat-sensitive surface layerisexposed with a flash lamp 9 through a transparent negative image 10 ofthe text to be reproduced. A smooth flat backing plate ll serves forsecuring a close adjustment with the diapositive. After the exposure themotion picture film is introduced by the guiding rollers 12 and 13 intothe washing bath 15 containing a selected treating liquid 16 forremoving the heated portions of the surface layer and containing etchingsubstances, e.g., sodium hypochlorite, for removing the silver or dyeoccasionally together with the binder of the emulsion layer(s) in theareas corresponding with the removed portions of the heat-sensitivesurface layer. The removal of the residual portions (the unexposedportions of the surface layer) proceeds by washing and rubbing in arinsing bath 19 contain- 1 ing the guiding rollers 17 and 18 and whereina solvent 20 continuously streams through and wherein a rubbing roller21 rotates in rubbing contact with the surface layer in oppositedirection to the motion direction of the film. Subsequently, the film isdried in a drying channel 22 and wound up on a takeup roller 23.

' Depending on the type of overlayer it can be necessary to use aseparate bath for the treating liquid and etching or bleaching solution.The selective removal of the overlayer can be speeded up by rubbing theoverlayer in wet state, e.g., in an apparatus described in the publishedDutch Pat. application No. 6,807,686.

For subtitling negative pictures with an opaque subtitle as alreadydescribed above as a first technique, an opaque overlayer can beapplied, which is heated in correspondence with the nonirnage parts of asubtitle to be reproduced, and the heated portions of the overlayerremoved leaving in that'way an opaque relief pattern of the opaqueoverlayer representing the desired subtitle information.

Compositions for preparing an opaque or colored overlayer which can beselectively removed in the heated portions by an aqueous treating liquidare the compositions mentioned under the numbers 1 to 11 of Table 1.Using such compositions and the technique of opaque subtitling describedabove no etching step and washing step for integral removal of theoverlayer has to be applied.

Although not strictly necessary, e".g., when using a colorlessoverlayer, it is preferred, after the subtitle has been formed, toremove the resist portions of the overlayer entirely. This can beaccomplished by dissolving the said portions, e.g., with the solvent orsolvent mixture, from which the overlayer has been coated.

The following examples illustrate the present invention.

EXAMPLE l The silver image-containing emulsion layer of an exposed anddeveloped silver halide photographic material was coated at a rate of 25g. per sq.m. with a covering layer prepared by ball milling thefollowing ingredients for 12 hours:

cresol-formaldehyde resin, type Novolalt (softening range -l05 C.) 200g. carbon black 15 g. ethanol L130 cc.

water 280 cc. Javelle water, comprising approxi mately I20 g. of activechlorine and 4 g. of sodium hydroxide per liter cc. l N sodium hydroxide20 cc.

The parts of the covering layer and the subjacent silver imagecontaining emulsion layer, which correspond with the light-struck areas,where then removed by rubbing with a plug of wadding. The material wasthen dipped again for sec. in the abovegdescribed etching bath. Finallythe whole covering layer was removed by treating with a plug of waddingsoaked with ethanol and rinsed with water.

EXAMPLE 2 A color developed Gevacolor (registered trade name) 16- mm.film was provided with the covering layer described in Example 1. Thematerial was exposed for 0.008 sec. by means of a flash lamp, receivingan energy output of 1.03 watt.sec/sq.cm. The exposed material was thendipped first, for 60 sec. in a 0.6 percent solution of sodium hydroxidein water and subsequently dipped for 40 sec. in a solution of Javellewater containing approximately 30 g. of active chlorine and 1 g. ofsodium hydroxide per liter. The covering layer was then removed withethanol. Finally, the material was rinsed with water.

As a result of the imagewise degrading of the gelatin, a relief image ofthe subtitle was produced on the film.

EXAMPLE 3 A developed duplicating negative motion picture film wascovered at a rate of 40 g. per sq.m. with a heatsensitive layer preparedby ball-milling the following ingredients for 12 hours:

ethanol L640 cc. poly( l ,2-dihydro-2,2,4-trimethylquinoline) 45 g.polyacrylic acid 100 3. carbon black 45 g.

2 g. 1 cc.

water Carbidschwarz E (C.l. 30,235) 25% solution of ammonia in waterNext the dipped material was rinsed with water and the rest of thecovering layer removed by means of a plug of wadding soaked with a 5percent solution of acetic acid in water.

Finally after rinsing with water and drying a negative motion picturefilm containing on the emulsion side in the picture frames a blueblackreproduction of a subtitle was obtained.

EXAMPLE 4 A developed duplicating negative motion picture film wasprovided at a rate of 32 g. per sq.m. with a heat-sensitive coveringlayer containing the following ingredients:

PAREZ RESIN 68 (a 80% by weight aqueous dispersion ofadimethyltrimethylolmclamine-forrnaldehyde resin sold by AmericanCyanarnid Comp.. New York, N.Y.. U.S.A.) I00 3.

poly(N-vinylpyrrolidone) 4 8- water 7l6 cc. ascorbic acid 8- aqueouscarbon black dispersion con taining per l00 g. :53 g. ofcarbon.

23 g. of water, l8 g. of ethylene glycol and 6 g. of nonylphenylpoly(ethylcne oxide),-,, l00 g. isooctylphenyl poly(ethylene 0xide) 10%in water 70 cc.

After drying of the coated layer at 90 C., the material was exposed for0.008 sec. through a transparent positive image of a subtitle by meansof a flash lamp, receiving an energy output of 0.80 watt.sec./sq.cm.

The exposed parts of the covering layer were then removed by rubbingwith a plug of wadding soaked with water.

The the negative images of the motion picture film a black reproductionof the subtitle was superposed.

EXAMPLE 5 A novolak consisting of the copolycondensate of equal molarparts of phenol and p-tert.butylphenol was prepared as follows.

ln the three-necked flask of 2 l. equipped with a strong stirrer, areflux condenser and a thermometer, a solution was prepared by mixing:

demineralised water 300 cc. anhydrous oxalic acid 10 g. freshlydistilled phenol 94 g. p-tert.butylphenol ISO 3. 37.5% aqueous solutionof formaldehyde I26 cc.

The mixture was allowed to react and refluxed for 3 hr. with stirring atll5l20 C. Then 20 cc. of concentrated hydrochloric acid (d=l.l9) wereadded, whereupon the mixture was refluxed for further 4 hr.

From the obtained pasty melt the water was decanted. The resin waswashed thrice with 500 cc. of boiling water, and then dehydrated underreduced pressure till a temperature of l45l50 C. was reached. The liquidresin was poured into a cooled metal dish, wherein it could easily bepulverized.

Yield: percent.

Softening point: 1 15120 C.

50 g. of this novolak were ball-milled for 8 hrs. with 5 g. of carbonblack in 450 g. of isopropanol. The fine dispersion obtained was thenapplied to the emulsion side of a developed positive silver image motionpicture film in a proportion of 50 g. per sq.m. After drying, thecovering layer thus formed was exposed for 0.004 sec. through a negativetransparency of the subtitle to be reproduced by means of a flash lamp,receiving an energy output of 0.77 watt.sec./sq.cm. Thereupon the filmwas first dipped in 0.6 aqueous sodium hydroxide solution for 20 sec.,shortly rinsed with pure water and finally for 25 sec. dipped into asolution of Javelle water containing per litre about 30 g. of activechlorine and l g. of sodium hydroxide. The film was then again rinsedshortly in pure water and the covering layer eliminated with ethanol.After drying, as a result of imagewise degradation of gelatin, atransparent pattern and a relief print of the subtitle to be reproducedwere obtained in the emulsion layer of the film.

EXAMPLE 6 Example 5 was repeated, but after exposure the coated positivemotion picture film was treated as follows:

dipping in 0.6 percent aqueous solution of sodium hydroxide for 20 sec.;

shortly rinsing in water;

dipping in the bleaching-fixing bath of the following composition for 25sec.:

iron(lll)chelate of the monosodium salt of ethylenediaminetetraaceticacid 60 g. anhydrous sodium carbonate 5 g. potassium bromide 30 g.potassium thiocyanate l0 g. sodium thiosulphate-S-water I40 g.demineralised water to L000 cc.

shortly rinsing in water elimination of the covering layer by means ofethanol rinsing in water and drying.

By imagewise eliminating the silver from the emulsion'layer, atransparent copy was obtained of the subtitle to be reproduced.

We claim:

1. A method of recording graphic information on a recording materialalready containing an image, comprising the steps of: coating the imageside of said material with a composition consisting essentially of anorganic film-forming polymer which upon heating undergoes an increase insolubility in a correspondingly selected solvent and uniformlydistributed finely divided particles of a pigment or dye capable ofabsorb: ing copying light and converting the same to heat; exposing saidimage side of said material to an image of copying light for less thanabout 0.1 sec., said light being of such intensity as to produce in saidsurface layer by the absorption and conversion thereof by said finelydivided particles sufficient heat to cause the heated areas of saidsurface layer to undergo said change in solubility; and contacting saidexposed surface layer with said selected solvent to substantially removesaid heated areas of said surface layer while leaving the unheated areasessentially intact.

2. A method of recording as in claim 1 wherein said material is ablack-and-white or color photographic material, the image of which isformed by means of at least one light-sensitive silver halide emulsionlayer,

3. A method according to claim 1 wherein said organic filmformingpolymer undergoes an increase in solubility in water in response toheating and is selected from the group consisting of:

galactomannan;

a cationic hydroxypropyl-starch;

a hydroxypropylmethyl-cellulose;

a cellulose acetate butyrate;

a melamine-formaldehyde resin, a methylol-melamine resin;

or an etherified methylol-melamine resin of the watersoluble type, whichresins are partially hardened after coating;

an anionic water-soluble urea-formaldehyde resin, which is partiallyhardened after coating;

a resorcinal-formaldehyde resin soluble in ethanol or in mixture ofwater and ethanol; and which becomes soluble in water by heating;

a composition containing a water-soluble polyvinyl alcohol mixed with ahardening agent containing reactive carbonyl groups;

a composition containing a poly( l,2-dihydro-2,2,4-

trimethylquinoline) and an acidic compound;

a water-soluble polymer or copolymer of an a, B-ethylenicallyunsaturated compound containing at least one carboxylic acid group andin admixture therewith cobalt naphthenate or dihydroxy benzophenoneforming a product with said unsaturated compounds that is less solublein water than the a, B-ethylenically unsaturated compound and that onheating dissociates resulting in an increase of the solubility in waterof the composition; and

an aiginic acid ester.

4. A method according to claim 1 wherein said organic filmforrningpolymer undergoes an increase in solubility in an alkaline aqueousmedium in response to heating and is selected from the group consistingof:

a novalak-type resin;

a polymer containing an azogroup linked through a carbon atom to anitrile group;

poly( N-vinylpyrrolidone); and

crude and/or bleached natural shellac.

5. A method according to claim 1 wherein said organic filmfonningpolymer undergoes an increase in solubility in a C -C alkanol inresponse to heating and is selected from the group consisting of:

poly( l,2-dihydro-2,2,4-trimethylquinoline);

a composition containing poly(N-vinylpyrrolidone) and amelamine-formaldehyde resin having methylol groups;

a composition containing polyvinyl alcohol or a partially hydrolizedpolyvinyl acetate mainly containing vinyl alcohol units, mixed with aquinone-diazide compound and an aldehyde or latent aldehyde splittingoff formaldehyde on heating; and

a copoly(styrene/N-vinylpyrrolidone) applied from a latex.

6. A method according to claim 1 wherein said organic filmfon'ningpolymer undergoes an increase in solubility in a lower ketone containingup to 4 carbon atoms linked to the carbonyl group in response to heatingand is selected from the group consisting of:

a copoly(styrene/N-vinylpyrrolidone) applied from a latex and a copoly(styrene/ acrylate ester). 7. A method according to claim 1 wherein saidorganic filrnforming polymer undergoes an increase in solubility in achlorinated aliphatic hydrocarbon solvent in response to heat ing and isselected from the group consisting of:

a composition containing a copoly(butadiene/styrene) and ano-quinone-diazide compound which decomposes to form an acid when heated;and a composition containing a phenol-formaldehyde resin and a peroxidecompound; is imagewise heated in the areas corresponding with thegraphic information to be recorded, and

is treated with a suitable treating liquid, by means of which the heatedportions of the surface layer are removed and/or permeated.

8. A method according to claim 1, wherein the said surface layer isirradiated for a period less than about 0.01 second and with an energyof at least 0.1 watt.sec./sq.cm.

9. A method according to claim 8, wherein said copying light containsvisible and infrared light.

10. A method according to claim 1, wherein the recording is ablack-and-white or a color motion picture film and the graphicinformation to be recorded is a subtitle.

11. A method according to claim 10, wherein the film contains positiveimages in a developed silver halide emulsion layer and the surface layeris exposed through a negative image of a subtitle before treatment withsaid liquid.

12. A method according to claim 11, wherein the surface layer during orafter its treatment with the selected liquid is contacted with anaqueous liquid, which has an etching or bleaching effect on the metallicsilver or a bleaching effect on dye forming the image in the developedemulsion layer.

13. A method according to claim 11, wherein the surface layer during orafter its treatment with the selected liquid is contacted with anaqueous liquid, which disintegrates the binder of a developed silverhalide emulsion layer.

14. A method according to claim 13, wherein the aqueous liquid fordisintegrating the developed silver halide emulsion layer contains ahypochlorite of an alkaline or an alkaline earth metal.

15. A method according to claim 10, wherein the film contains negativeimages and the surface layer is exposed through a negative image of asubtitle before treatment with said liquid.

16. A method according to claim 15, wherein the surface layer during orafter its treatment with said liquid is treated with an aqueous liquid,which produces a coloration in an underlying layer.

17. A method according to claim 10, wherein the blackand-white or colormotion picture film contains negative images and said surface layercontains sufficient pigment or dye as to be generally opaque and isexposed to a positive copying light image of said subtitle so that theareas of the surface layer that correspond to the nonimage parts of thesubtitle undergo said increase in solubility and are removed when thelayer is contacted with said liquid, thereby leaving an opaque pigmentedor dyed relief pattern representing the subtitle on the film.

18. The method of claim 17 wherein said dye or pigment is present insufficient amount to impart to the surface layer an optical density ofat least 1.

19. A method for applying graphic information to a recording orreproduction material already containing an image according to claim 1,comprising the steps of: (1) coating the image layer side of saidmaterial with a surface layer essentially consisting of aphenol-formaldehyde, cresol-formaldehyde,p-tert.butylphenol-formaldehyde or mixed monohydroxybenzenehomologueformaldehyde novolak mixed with a finely divided infraredand/or visible light-absorbing substance or mixture of substancesconverting absorbed light into heat; (2) image-wise irradiating saidsurface layer with infrared and/or visible light of a sufficient energyto increase its solubility in an aqueous alkaline medium, and (3)treating the imagewise exposed surface layer with an aqueous alkalineliquid selectively removing thereby the exposed portions of the surfacelayer.

2. A method of recording as in claim 1 wherein said material is ablack-and-white or color photographic material, the image of which isformed by means of at least one light-sensitive silver halide emulsionlayer,
 3. A method according to claim 1 wherein said organicfilm-forming polymer undergoes an increase in solubility in water inresponse to heating and is selected from the group consisting of:galactomannan; a cationic hydroxypropyl-starch; ahydroxypropylmethyl-cellulose; a cellulose acetate butyrate; amelamine-formaldehyde resin, a methylol-melamine resin; or an etherifiedmethylol-melamine resin of the water-soluble type, which resins arepartially hardened after coating; an anionic water-solubleurea-formaldehyde resin, which is partially hardened after coating; aresorcinal-formaldehyde resin soluble in ethanol or in a mixture ofwater and ethanol; and which becomes soluble in water by heating; acomposition containing a water-soluble polyvinyl alcohol mixed with ahardening agent containing reactive carbonyl groups; a compositioncontaining a poly(1,2-dihydro-2,2,4-trimethylquinoline) and an acidiccompound; a water-soluble polymer or copolymer of an Alpha , Beta-ethylenically unsaturated compound containing at least one carboxylicacid group and in admixture therewith cobalt naphthenate or dihydroxybenzophenone forming a product with said unsaturated compounds that isless soluble in water than the Alpha , Beta -ethylenically unsaturatedcompOund and that on heating dissociates resulting in an increase of thesolubility in water of the composition; and an alginic acid ester.
 4. Amethod according to claim 1 wherein said organic film-forming polymerundergoes an increase in solubility in an alkaline aqueous medium inresponse to heating and is selected from the group consisting of: anovalak-type resin; a polymer containing an azogroup linked through acarbon atom to a nitrile group; poly(N-vinylpyrrolidone); and crudeand/or bleached natural shellac.
 5. A method according to claim 1wherein said organic film-forming polymer undergoes an increase insolubility in a C1-C3 alkanol in response to heating and is selectedfrom the group consisting of:poly(1,2-dihydro-2,2,4-trimethylquinoline); a composition containingpoly(N-vinylpyrrolidone) and a melamine-formaldehyde resin havingmethylol groups; a composition containing polyvinyl alcohol or apartially hydrolized polyvinyl acetate mainly containing vinyl alcoholunits, mixed with a quinone-diazide compound and an aldehyde or latentaldehyde splitting off formaldehyde on heating; and acopoly(styrene/N-vinylpyrrolidone) applied from a latex.
 6. A methodaccording to claim 1 wherein said organic film-forming polymer undergoesan increase in solubility in a lower ketone containing up to 4 carbonatoms linked to the carbonyl group in response to heating and isselected from the group consisting of: acopoly(styrene/N-vinylpyrrolidone) applied from a latex and acopoly(styrene/acrylate ester).
 7. A method according to claim 1 whereinsaid organic film-forming polymer undergoes an increase in solubility ina chlorinated aliphatic hydrocarbon solvent in response to heating andis selected from the group consisting of: a composition containing acopoly(butadiene/styrene) and an o-quinone-diazide compound whichdecomposes to form an acid when heated; and a composition containing aphenol-formaldehyde resin and a peroxide compound; is imagewise heatedin the areas corresponding with the graphic information to be recorded,and is treated with a suitable treating liquid, by means of which theheated portions of the surface layer are removed and/or permeated.
 8. Amethod according to claim 1, wherein the said surface layer isirradiated for a period less than about 0.01 second and with an energyof at least 0.1 watt.sec./sq.cm.
 9. A method according to claim 8,wherein said copying light contains visible and infrared light.
 10. Amethod according to claim 1, wherein the recording is a black-and-whiteor a color motion picture film and the graphic information to berecorded is a subtitle.
 11. A method according to claim 10, wherein thefilm contains positive images in a developed silver halide emulsionlayer and the surface layer is exposed through a negative image of asubtitle before treatment with said liquid.
 12. A method according toclaim 11, wherein the surface layer during or after its treatment withthe selected liquid is contacted with an aqueous liquid, which has anetching or bleaching effect on the metallic silver or a bleaching effecton dye forming the image in the developed emulsion layer.
 13. A methodaccording to claim 11, wherein the surface layer during or after itstreatment with the selected liquid is contacted with an aqueous liquid,which disintegrates the binder of a developed silver halide emulsionlayer.
 14. A method according to claim 13, wherein the aqueous liquidfor disintegrating the developed silver halide emulsion layer contains ahypochlorite of an alkaline or an alkaline earth metal.
 15. A methodaccording to claim 10, wherein the film contains negative images and thesurface layer is exposed through a negative image of a subtitle beforetreatment with said liquid.
 16. A method according to claim 15, whereinthe surface layer during or after its treatment with said liquid istreated with an aqueous liquid, which produces a coloration in anunderlying layer.
 17. A method according to claim 10, wherein theblack-and-white or color motion picture film contains negative imagesand said surface layer contains sufficient pigment or dye as to begenerally opaque and is exposed to a positive copying light image ofsaid subtitle so that the areas of the surface layer that correspond tothe nonimage parts of the subtitle undergo said increase in solubilityand are removed when the layer is contacted with said liquid, therebyleaving an opaque pigmented or dyed relief pattern representing thesubtitle on the film.
 18. The method of claim 17 wherein said dye orpigment is present in sufficient amount to impart to the surface layeran optical density of at least
 1. 19. A method for applying graphicinformation to a recording or reproduction material already containingan image according to claim 1, comprising the steps of: (1) coating theimage layer side of said material with a surface layer essentiallyconsisting of a phenol-formaldehyde, cresol-formaldehyde,p-tert.butylphenol-formaldehyde or mixed monohydroxybenzenehomologueformaldehyde novolak mixed with a finely divided infraredand/or visible light-absorbing substance or mixture of substancesconverting absorbed light into heat; (2) image-wise irradiating saidsurface layer with infrared and/or visible light of a sufficient energyto increase its solubility in an aqueous alkaline medium, and (3)treating the imagewise exposed surface layer with an aqueous alkalineliquid selectively removing thereby the exposed portions of the surfacelayer.